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NASA NTRS2016

Interpreting Space-Based Trends in Carbon Monoxide with Multiple Models

We use a series of chemical transport model and chemistry climate model simulations to investigate the observed negative trends in MOPITT CO over several regions of the world, and to examine the consistency of timedependent emission inventories with observations. We find that simulations driven by the MACCity inventory, used for the Chemistry Climate Modeling Initiative (CCMI), reproduce the negative trends in the CO column observed by MOPITT for 2000-2010 over the eastern United States and Europe. However, the simulations have positive trends over eastern China, in contrast to the negative trends observed by MOPITT. The model bias in CO, after applying MOPITT averaging kernels, contributes to the model-observation discrepancy in the trend over eastern China. This demonstrates that biases in a model's average concentrations can influence the interpretation of the temporal trend compared to satellite observations. The total ozone column plays a role in determining the simulated tropospheric CO trends. A large positive anomaly in the simulated total ozone column in 2010 leads to a negative anomaly in OH and hence a positive anomaly in CO, contributing to the positive trend in simulated CO. These results demonstrate that accurately simulating variability in the ozone column is important for simulating and interpreting trends in CO.

carbon monoxide↗

NASA NTRS2020

Global earth mineral inventory: A data legacy

Minerals contain important clues to understanding the complex geologic history of Earth and other planetary bodies. Therefore, geologists have been collecting mineral samples and compiling data about these samples for centuries. These data have been used to better understand the movement of continental plates, the oxidation of Earth's atmosphere and the water regime of ancient martian landscapes. Datasets found at ‘RRUFF.info/Evolution’ and ‘mindat.org’ have documented a wealth of mineral occurrences around the world. One of the main goals in geoinformatics has been to facilitate discovery by creating and merging datasets from various scientific fields and using statistical methods and visualization tools to inspire and test hypotheses applicable to modelling Earth's past environments. To help achieve this goal, we have compiled physical, chemical and geological properties of minerals and linked them to the above-mentioned mineral occurrence datasets. As a part of the Deep Time Data Infrastructure, funded by the W.M. Keck Foundation, with significant support from the Deep Carbon Observatory (DCO) and the A.P. Sloan Foundation, GEMI (‘Global Earth Mineral Inventory’) was developed from the need of researchers to have all of the required mineral data visible in a single portal, connected by a robust, yet easy to understand schema. Our data legacy integrates these resources into a digestible format for exploration and analysis and has allowed researchers to gain valuable insights from mineralogical data. GEMI can be considered a network, with every node representing some feature of the datasets, for example, a node can represent geological parameters like colour, hardness or lustre. Exploring subnetworks gives the researcher a specific view of the data required for the task at hand. GEMI is accessible through the DCO Data Portal (https://dx.deepcarbon.net/11121/6200-6954-6634-8243-CC). We describe our efforts in compiling GEMI, the Data Policies for usage and sharing, and the evaluation metrics for this data legacy.

data legacy↗

NASA NTRS2001

Self-Assembling Amphiphilic Molecules: A Possible Relationship Between Interstellar Chemistry and Meteoritic Organics

Interstellar gas and dust comprise the primary material from which the solar system formed. Evidence that some of this material was organic in nature and survived incorporation into the protosolar nebula is provided by the presence of deuterium-enriched organics in meteorites and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall of meteoroids and cosmic dust must have seeded them with some of these complex organic compounds. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by ultraviolet (UV) photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

Sandford, Scott A.↗

NASA NTRS2001

Self-assembling amphiphilic molecules: Synthesis in simulated interstellar/precometary ices

Interstellar gas and dust constitute the primary material from which the solar system formed. Near the end of the hot early phase of star and planet formation, volatile, less refractory materials were transported into the inner solar system as comets and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall seeded them with complex organic compounds [Oro, J. (1961) Nature (London) 190, 389-390; Delsemme, A. H. (1984) Origins Life 14, 51-60; Anders, E. (1989) Nature (London) 342, 255-257; Chyba, C. F. & Sagan, C. (1992) Nature (London) 355, 125-131]. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by UV photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

Meteoroids↗

NASA NTRS2003

The Organic Component of Interstellar Dust

The distribution, chemical structure, and formation of organic matter in the interstellar medium are important to our understanding of the overall evolution of dust. The exchange of dust between the dense and diffuse interstellar medium, and the effects of processing on dust within dense clouds will affect the inventory of material available for incorporation into newly forming star and planetary systems. Observational ground-based studies have confirmed the widespread distribution of the 3.4 pm absorption band attributed to aliphatic hydrocarbons in the diffuse interstellar medium of our own galaxy, and in the dusty spectra of a few nearby galaxies, while space based observations from IS0 probed the signatures of corresponding mid-infrared features. Laboratory experiments which utilize both thermal processes and energetic processing by high energy photons and cosmic rays, produce candidate materials which offer close matches to the observed diffuse interstellar medium and extragalactic hydrocarbon absorption features. Through an analysis of the 4000 to 1000 cm (2.5 to 10 micrometers) region of the spectrum of diffuse interstellar medium (DISM) dust compared with the spectra of thirteen chemical entities produced in the laboratory which serve as analogs to the interstellar material, significant constraints have been placed on the applicability of proposed candidate materials to explain the interstellar features. The results indicate that the organic refractory material in the diffuse interstellar medium is predominantly hydrocarbon in nature, possessing little nitrogen or oxygen, with the carbon distributed between the aromatic and aliphatic forms. Long alkane chains H3C-(CH2),- with n much greater than 4 or 5 are not major constituents of this material. Comparisons to laboratory analogs indicate the DISM organic material resembles plasma processed pure hydrocarbon residues much more so than energetically processed ice residues. This result is consistent with a birthsite for the carrier of the 3.4 micrometers band in the outflow region of evolved carbon stars. Comparisons of dust from our own galaxy with that of distant galaxies suggests that the organic component of interstellar dust is widespread and may be an important universal reservoir of prebiotic organic carbon.

Pendleton, Yvonne↗

NASA NTRS1982

Conference on Planetary Volatiles

Initial and present volatile inventories and distributions in the Earth, other planets, meteorites, and comets; observational evidence on the time history of volatile transfer among reservoirs; and volatiles in planetary bodies, their mechanisms of transport, and their relation to thermal, chemical, geological and biological evolution were addressed.

Hrametz, K.↗

NASA NTRS1982

Conference on Planetary Volatiles

Pepin, R. O.↗

NASA NTRS2000

Computing Needs for Astrobiology: Models of Planetary Formation

Theories of planet formation indicate that a diverse range of physical and chemical processes determine the characteristics of a planetary system. Extensive numerical modeling is required to understand how planetary systems form, and to make quantitative assessments of the factors which determine the masses, spacings and volatile compound inventories of planets and small bodies within a planetary system. Fluid flow problems associated with the formation and evolution of protoplanetary disks include specific local calculations to provide physical insight, which are best performed on workstations, and large multifaceted simulations which require supercomputers with large memories. Formation and early growth of planetesimals display a similar range of computational requirements. Modeling the late stages of planetary accumulation is very CPU intensive, as it requires following a simple system of approx. hundreds of bodies for millions of dynamical (orbital) times. These varied computational needs could be met in the most cost-effective manner by a diverse set of computers, including workstations for individual PI's and dedicated time on various types of supercomputers which are specialized for differing tasks.

Lissauer, Jack J.↗

NASA NTRS2022

Evaluating the Impact of Chemical Complexity and Horizontal Resolution on Tropospheric Ozone Over the Conterminous US With a Global Variable Resolution Chemistry Model

A new configuration of the Community Earth System Model (CESM)/Community Atmosphere Model with full chemistry (CAM-chem) supporting the capability of horizontal mesh refinement through the use of the spectral element (SE) dynamical core is developed and called CESM/CAM-chem-SE. Horizontal mesh refinement in CESM/CAM-chem-SE is unique and novel in that pollutants such as ozone are accurately represented at human exposure relevant scales while also directly including global feedbacks. CESM/CAM-chem-SE with mesh refinement down to ∼14 km over the conterminous US (CONUS) is the beginning of the Multi-Scale Infrastructure for Chemistry and Aerosols (MUSICAv0). Here MUSICAv0 is evaluated and used to better understand how horizontal resolution and chemical complexity impact ozone and ozone precursors over CONUS as compared to measurements from five aircraft campaigns, which occurred in 2013. This field campaign analysis demonstrates the importance of using finer horizontal resolution to accurately simulate ozone precursors such as nitrogen oxides and carbon monoxide. In general, the impact of using more complex chemistry on ozone and other oxidation products is more pronounced when using finer horizontal resolution where a larger number of chemical regimes are resolved. Large model biases for ozone near the surface remain in the Southeast US as compared to the aircraft observations even with updated chemistry and finer horizontal resolution. This suggests a need for adding the capability of replacing sections of global emission inventories with regional inventories, increasing the vertical resolution in the planetary boundary layer, and reducing model biases in meteorological variables such as temperature and clouds.

MUSICA↗

NASA NTRS1991

Lunar surface - Sputtering and secondary ion mass spectrometry

Laboratory and Apollo observations are combined to describe the sputtering of the lunar surface and the composition of the ejecta with special reference to O. The atmospheric inventory appears to be dominated by micrometeorite vaporization of lunar grains. Sputtering effects are observable in the local plasma due to ion ejection, in the extended atmosphere through energetic neutral ejection, and on grain surfaces through the chemical fractionation of the redoposited sputter-ejecta. Ionization of the micrometeorite-vapor also contributes to the local plasma.

Johnson, R. E.↗

NASA NTRS1985

Venus, Earth and Mars: Present bounds on similarities and differences in bulk composition

The bulk compositions of the terrestrial planets are constrained in part by rigorous bounds derivable from geophysical data and from chemical data obtained in situ or by remote sensing. In large part, however, the bulk compositions are constrained only by the inferred plausibility of assumptions made about the processes responsible for producing planets. Present data are consistent with Venus, Earth and Mars all having solar ratios of the major, non-volatile elements. The mantle of Mars has a higher FeO content than the Earth's present upper mantle. The FeO content of the Venus mantle is poorly constrained. Abundances of minor elements are virtually unconstrained by geophysical data and only weakly constrained by existing chemical data. Inferences drawn from SNC meteorites suggest that Mars may be enriched in most volatiles relative to the Earth. Simple models in which volatiles are added in a single component probably do not accurately predict bulk volatile inventories of the planets.

Goettel, K. A.↗

NASA NTRS2012

Atmospheric Prebiotic Chemistry and Organic Hazes

Earth's atmospheric composition at the time of the origin of life is not known, but it has often been suggested that chemical transformation of reactive species in the atmosphere was a significant source of pre biotic organic molecules. Experimental and theoretical studies over the past half century have shown that atmospheric synthesis can yield molecules such as amino acids and nucleobases, but these processes are very sensitive to gas composition and energy source. Abiotic synthesis of organic molecules is more productive in reduced atmospheres, yet the primitive Earth may not have been as reducing as earlier workers assumed, and recent research has reflected this shift in thinking. This work provides a survey of the range of chemical products that can be produced given a set of atmospheric conditions, with a particular focus on recent reports. Intertwined with the discussion of atmospheric synthesis is the consideration of an organic haze layer, which has been suggested as a possible ultraviolet shield on the anoxic early Earth. Since such a haze layer - if formed - would serve as a reservoir for organic molecules, the chemical composition of the aerosol should be closely examined. The results highlighted here show that a variety of products can be formed in mildly reducing or even neutral atmospheres, demonstrating that contributions of atmospheric synthesis to the organic inventory on early Earth should not be discounted. This review intends to bridge current knowledge of the range of possible atmospheric conditions in the prebiotic environment and pathways for synthesis under such conditions by examining the possible products of organic chemistry in the early atmosphere.

Trainer, Melissa G.↗

NASA NTRS2022

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗

NASA NTRS1997

Analyses of Scenarios for Past and Possible Future Aircraft Emissions

This project contains several components to work with the NASA AEAP program in better definition of scenarios for aircraft emissions and in determining the sensitivity of the atmosphere to such emissions. Under this project, Don Wuebbles continues as chair of the Operations and Emissions Scenarios Committee for AEAP. We are also coordinating with the International Civil Aviation Organization (ICAO) to ensure the highest quality possible in the emissions scenarios promoted by the Emissions Scenarios committee. We continue to help coordination of NASA AEAP with international activities. This includes work with ICAO towards international analysis of aircraft emissions inventories; performing analyses to compare and evaluate databases of aircraft emissions developed for NASA and by various international groups and from these analyses, develop guidelines for future emissions scenarios development. Special sensitivity analyses, using our two-dimensional chemical-transport model of the global troposphere and stratosphere, have been used to determine potential sensitivity of further enhancements that could be made to emissions scenarios development. The latter studies are to be used in prioritizing further emissions scenario development.

Wuebbles, Donald J.↗

NASA NTRS1989

Meteoritic silicon carbide and its stellar sources - Implications for galactic chemical evolution

Interstellar silicon carbide grains in meteorites provide a novel means for studying the carbon-star population of about 5 x 10 to the 9th years ago. Their C-12/C-13 ratios differ greatly from the solar value but resemble those of present-day csrbon stars, implying little change in the galactic C-13 inventory. Isotope data on nitrogen and silicon suggest that the silicon carbide grains come mainly from red giants, with small contributions from novae.

Ming, Tang↗

NASA NTRS1990

Ammonia and nitrogen abundances in comets

Comets consist of pristine material preserved from an earlier galactic epoch. Determination of the molecular, elemental, and isotopic abundances in the dust and volatile components of comet nuclei produce vital clues to the chemical evolution of both interstellar and solar nebula matter. Here the abundances of nitrogen-containing molecules in comets are considered. The molecular abundances of NH3 in four comets are summarized (Tegler 1990, Wyckoff, Tegler, and Engel, 1990). From an inventory of nitrogen-containing compounds (Wyckoff, Engel, and Tegler 1990, Wyckoff, Engel, Womack, Ferro, Tegler and Peterson, 1990), an estimate of the elemental N abundance is also presented.

Wyckoff, Susan↗

NASA NTRSDate not supplied

A window on the composition of the early solar nebula: 2014MU69, Pluto, and Phoebe

The initial chemical composition of any solar nebula will depend upon the degree to which 1) organic and ice components form on dust grains, 2) organic and molecular species form in the gas phase, 3) organics and ices are exchanged between the gas and solid state, and 4) the precursor and newly formed (more complex) materials survive and are modified in the developing planetary system. Infrared and radio observations of star-forming regions reveal that complex chemistry occurs on icy grains, sometimes before stars even form. Additional processing, through the protosolar disk and within the solar nebula further modifies most, but probably not all, of the initial materials. In fact, the modern Solar System still carries a fraction of its interstellar inheritance [Alexander et al., 2017]. Here we focus on three examples of small bodies in our Solar System, each containing chemical and dynamical clues to its origin and evolution: the small, cold-classical Kuiper Belt object (KBO) 2014MU69 , Pluto and Saturn’s moon, Phoebe. The New Horizons flyby of 2014 MU69 has given the first view of an unaltered body composed of material originally in the solar nebula at ~45 AU. The spectrum reveals methanol ice (not commonly found), a possible detection of water ice (Stern et al. 2019). Pluto’s internal and surface inventory of volatiles and complex organics, together with active geological processes including cryo-volcanism, indicate a surprising level of activity on a body in the outermost region of the Solar System, and the fluid that emerges from subsurface reservoirs may contain material inherited from the solar nebula (Cruikshank et al. 2019). Meanwhile, Saturn's captured moon, Phoebe, carries high D/H in H2O [Clark et al. 2018)], and complex organics (Cruikshank et al. 2008), both consistent with its formation in, and inheritance from, the outer solar nebula. Together, these objects provide windows on the origin and evolution of our Solar System and constraints to be considered in future chemical and physical models of PPDs. The Spitzer Space telescope discovered the ring of dust around Saturn that emanated from the bombardment of Phoebe in the recent past, dislodging primitive Solar System material from deep within that satellite. In addition, Spitzer has provided detailed studies of the chemistry of star forming regions where methanol and other ices are readily observed. As a result of these and other observations, protoplanetary disk models are beginning to combine both dynamical and chemical complexities into their codes, resulting in new insights for exoplanetary systems.

Yvonne J. Pendleton↗

NASA NTRS2012

Amino Acids in Asteroids and Comets: Implications for the Origin of Life on Earth and Possibly Elsewhere

Meteorites provide a record of the chemical processes that occurred in the early solar system before life began on Earth. The delivery of organic matter by asteroids, comets, and their fragments to the Earth and other planetary bodies in our solar system could have been an important source of the prebiotic organic inventory needed for the emergence of life. Amino acids are essential components of proteins and enzymes in life on Earth and these prebiotic organic compounds have been detected in a wide variety of carbon-rich meteorites, the majority of which have been determined to be extraterrestrial in origin. In addition, many amino acids are structurally chiral (they possess handedness) and with a few very rare exceptions, only left handed (L) amino acids are found in biology, while all known abiotic syntheses of amino acids result in equal mixtures of left and right handed (L~D) amino acids. The discovery of a significant left handed amino acid imbalance of up to 20% in several different carbonaceous meteorites, could point toward a possible prebiotic contribution to the origin of biological homochirality by the exogenous delivery of extraterrestrial organic material to the early Earth. In this talk, I will focus on recent state-of-the-art measurements of the distribution, chirality, and isotopic composition of amino acids in meteorites and cometary samples carried out at the Goddard Astrobiology Analytical Laboratory. Results from the analyses of a variety of Antarctic meteorites, samples from comet Wild 2 returned by the STARDUST mission, and meteorite fragments of asteroid 2008 TC3 called Almahata Sitta recovered from northern Sudan will be discussed

Glavin, Daniel↗